Catalytic conversion of hydrocarbons



P. 1 vELTMA'N 2,394,412

CATALYTIC CONVERSION .OF HYDROGARBONS Filed May 41. 194s 2 sheets-sheet 1 .VN IM'N.) @N Q.I NP e ouwumaww m- ...l NN L n .Feb. 5; v1946.

om tz: a ZO- .FEO-.P041 m& 0L /UJUrUNm U I 4Feb. 5, 94@ P. I.. vr-:LTMAN CATALYTIG CONVERSION OF' HYDROCARBONS Filed' May 4, 1943 2 Sheets-Sheet 2 II.IV|

IIIWI PRESTON LA VELTMAN IN V I NTO R ATTORNEY .complex and complex formed in situ.

Patented F eb.`5, 1946 UNITED AsTATlzs PATENT' OFFICE f cAraLY'rIc CONVERSION OF nynnooAaBoNs Preston L. Veltman, Port Arthur, Tex., assigner to The Texas Company, New York, N .Y.,a corporation of Delaware Application May 4, 1943, senaiN0.4s5,so4

5 Claims.

(ci. 26o-683.4)

Aluminum halides vform many diiIerent-types of addition compounds with hydrocarbons depending upon the nature of the hydrocarbons and V the conditions under which the reaction vis brought about. The compounds'so formed may4 be highly complex in nature. l

Y It hasbeen found, however, that aluminum I halide-hydrocarbon complex lmixtures of specithe reaction and which is catalytically active in effecting l' the principal conversion reaction' desired, or it may comprise a mixture of preformed Specically, the invention involvessubjecting the complex catalyst to washing with a suitable solvent so as to extract therefrom hydrocarbon material or other material such as water, oxygen or oxygen compounds that may be associated with the complex and which if not removed result in substantial ldeterioration'of the catalyst during the conversion reaction, or otherwise affect the reaction adversely.

During the course of conversion reactions such as isomerization and alkylation with liquid aluminum halide-hydrocarbon complex catalyst, inactive material of a complex nature or in the form of hydrocarbon residues may be formed through reaction between the catalyst and certain hydrocarbon constituents. of. the feed. Initially the products of these side reactions may be in loose combination with the catalyst and unless removed, chemically conden'se to form stable complex material which is catalytically-inactive. Accordingly, it is desirable to extract the unstable material from the catalyst before such condensation reactions occur.

Extraneous material such as oxygen, or Oxygen compounds formed within the .catalyst mass 4 through reaction with oxygen and hydrocarbons,

or products of side reactions in the presence of the catalyst, .may-lbs present in the catalyst and interfere with or adversely aiect the reaction to such an extent that it is extremely diiilcult, if not impossible to control properly the reaction.

For these reasons it is advantageous'to subject the complex catalyst to washing or scrubbing in order to remove the foregoing type of material which may include complex and non-complex material which by itself is catalytically inactive, but which exerts an adverse eiect or influence upon the activity of the catalyst with consequent decline .in the Vcatalyst activity.l ,zl'he washing treatment is also useful .in removing hydrocarbons which are highly susceptible' to cracking;

heat evolved.

iied character' are-eiiective as conversion catalysts for isomerization and alkylation.4 Therefore, it 'is important to preserve the character of the complex catalyst and avoid degradation with'consequent increase incatalyst consumption. -v

An effective catalyst for effecting isomerization reactions comprises aluminum halidefhydrocarbon complex which has a heat of hydrolysis within the range about 20.0 to 400, and preferably about 300v to 320 `calories per gram of complex. The heat of hydrolysis` isldetermined by mixing in a calorimeter at about normal room temperaturea small and measured quantity ofthe complex with a quantity of water (about 3 grams of complex per gram of water) and measuring the The complex is a ids that would be separatecl'by centrifuging at about 3000 revolutions per minute for a period of 1/2 hour in an A. P. I.' centrifuge at about normal room temperature. Also it is characterizedby cubic centimeter. y

A complex catalyst free from solid aluminum I halide-is advantageous because there is no loss weight of anhydrous aluminum chloride powder may be mixed with about 1600 parts by weight of the kerosene. To this mixture is added 450 Darts by weight of hydrogen chloride. The entire mixture is subjected to agitation in a closed lvessel for a period of about 4 hours ata temperature in the range -to about 200 F. The time of reaction may be shorter or longer depending upon the amount of hydrogen chloride employed as well as upon the temperature used.

Thereaction mixture is thereafter cooled and the contents separated into phases. The complex phase is removed from the hydrocarbon phase and in accordance with the present invention is washed or otherwise treated with a suitable'soldvantageously free from sol-4'` having a densityof about 1.35 to 1.45 grams per vent such aspropane, normal or iso butano. cyclopentane or normal pentane, carbon tetrachlov rideA or methylene chloride, etc., at a temperature ranging from about room temperature to 220 F. .The particular solvent selected mayl depend upon the nature/ of the conversion reaction from which the complex is derived. If the objectionable material to be .removed from the catalyst isv .formed through a combination of complex withwater, carbon dioxide, or .oxygen, solvents s'uch as carbon tetrachloride-or methylene chloride or other polar liquidlmay be used to dissolve and extract the objectionable material from the liquid catalyst. or partially disperse the complex and permit the undesired material to separate from the mixture Such solvents may befus'ed to dilute upon standing.. On the other hand if the objec tionable material is formed by 'reaction of the complex with oleiins. isoparalns, aromatica, etc., a solvent such as aN saturated hydrocarbon hav? ing up to about 4 or 5 carbon atoms per molecule with it and thereafter recycling the washed catalyst tothe reaction acne. M pointed out earlier, during the catalytic conversion reaction side reactions may occurwherein objectionable material forms or accumulates. Accordingly. by continuously withdrawing 'a portion of the complex catalyst vfrom the system, washing it with a solhydrocarbonsgbcontaining at least 5 carbon atom's per. molecule and wherein the withdrawn compl'ex catalyst is subjected to treatment with a lower molecular weight saturated' hydrocarbon may be used to wash out the objectionable molecules or fragments. A `It is contemplated that removal of the objec-A tionable molecular fragmentsfrcm the complex may involve a reaction such as alkylation.

such as normal or. iso butane for the purpose of .displacing objectionable hydrocarbon residues and inactive complex materialirom the catalyst.

It has been observed thata' complex catalyst of this 4 type when used for isomerizing Cs and The'washing may be eiected in batch'or in'.

a continuous-concurrent or countercurrent flow operation employing about 3 or'4 volumes of i solvent liquid toll volume oi complex.

'Removall of' residual kerosene from the foregoing preformed complex' is advantageous where higher, molecular .weight hydrocarbons may lose its' activity during continued use, loss of activity being reflected by a progressive decrease in the f degree of octane improvement in the converted hydrocarbons. During. this continued use a dethe -washed complex isN to be retained in stor-v age or is to be used as a conversion catalyst in a catalytic reaction involving 4a temperature higher Vthan 200 F."or higher than the temperature at which 4the complex is formed. Otherwise the re crease in the speciiic gravity of the complex weight from 1.5 or 1.4 to 1.3 is observed which indicates an increase in the hydrocarbon content of the complex. It is preferred to maintain the gravity of the complex at least about 1.35.

sidual kerosene ii.' not removed may undergo de'- composition in the subsequent catalytic reaction forming compounds which would enter into objectionable complex formation with halide contained irthe complex.

In the isomerization of normal butane, for exe The purpose of the butane treatment, therefore, is to restore the' activity',- and-this treatment besidesI eifecting displanementV of hy`- drocarbon residues or Aother inactive material from flthe complex may also involve alkylatio'n reactions aluminum ample, areaction' temperature ranging from 210 to 220 or. 230. F. is usually maintained. A ccordingly, when eiecting the isomerization, reaction with a preformedscomplex of kerosene and alu-t minun'rhalide it is contemplated ilrst washing the complex with a relatively low boiling hydrocarbon such as butane for the purpose.- of extracting and removingw residual kerosene hydrocarbons from the dcomplex. The washing is advantageo feed hydrocarbon to the catalytic isomerization reaction. A

I'he vpresence of 'excess hydrocarbons Vin prelformed kerosene complex seems to result in a eected with normal butane thereby oli-- taining a washed preformed complex saturated i4 with a hydrocarbon of the same character as the betweennormal or iso butane-and a-portion o! the vhydrocarbon material which has become complexed'with the aluminum halide during isomer.. izationof the higher molecular weight feed hydrocarbon. Such allwlation reactions may -be promoted by the action of the small amount of residual hydrogen chloride promoterlretained in the complex-catalyst as withdrawn from .the reractionzone. f

In order vto describe the invention further reference will nowbemade to the' figureeo'f theaccompanying drawings showing flow diagrams illustratingmethods of practicing the invention.

Referring afeed hydrocarbon such as normal pe e of hydrocarbons such as a -pentane-hexane fraction of straightand conducted through a.pipe`"i d a heater' l wherein' it is heated to a -tem ure of about decline-in -activity of the complex catalyst upon %0 21'11".V `'Il'ho -heated\"feed hydrocarbon is standing, the 7decline being indicated by, adc creasein the heat of hydrolysis. i

The amount or -extraen obtained by'extraeting volumes of normal pentaneat abouteroom'tem-- uma of the complex, andthe extract may .contain small amounts of solidv sidue including oxides of aluminum, iron and titanium; etc.

` The invention also eontemplates continuously' perature may range' from about 5 to 20% by'r'vol;v

then'introducedto the lower portion of reaction tower 3. 'I'he reaction towergv advan tageously .maintained illled with'a coluim'rof .la volume or preformed-kerosene extract with 3-6541111114 'cQmDleX @myst smh QS-Previously de:

scribed and in arelatlvely' quiescent orInon-f :agitated condition.

A portion of lthe feed stream is advantageously diverted vthrough a branch pipe 4 leading to the -top of an absorberfwherein itis brought 'into countercurrent contact with i a i 'gaseous promoter such as hydrogen chloride entering the bottom -of the absorber 5 from a pipe 6 to which reference 4 complexmaterial that may become -75 Theabscrbenmaybeopetedatia vertical `amounts of hydrogen chloride.

2,894,419 sistinsessentill'y of about.100 F. andthe amount of i'eed hydrocarbon diverted through the absorber is adjusted so as to pick up the required amount of promoter suiiicient for promoting the reaction in the reactor 3. Thus, the promoter added may amount to about from 0.1 to by weight of the total feed hydrocarbon. The resulting solution of feed hydrocarbon and promoter is drawn oil! from the bottom of the absorber 5 through a pipe 'I and a heater 8 from which the mixture is discharged to the reactor 3.

The feed hydrocarbon is introduced to the bot-l tom portion of the reaction tower so as to bubble upwardly through a non-mechanically agitated column of catalyst liquid in the presence of promoter. Y

The treated hydrocarbons including isomerized hydrocarbons accumulate above the surface of the liquid catalyst at the top of the reactor 3 and are continuously withdrawn therefrom through a pipe l' leading to a hydrogen chloride stripping tower 8'.

In the stripper 8 conditions are maintained so as to strip out of the isomerized hydrocarbon mixture hydrogen chloride contained therein. The hydrogen chloride together with a small amount of gaseous hydrocarbon material such as methane and ethane is continuously removed from the stripper through a pipe 9 and all or a portion thereof recycled through a branch pipe 6 previously designated as pipe 6.

The isomerized hydrocarbon mixture from which the hydrogen chloride hasI been stripped is conducted from the stripper through a pipe lu to a fractionation unit Il wherein the treated hydrocarbons may be separated into fractions as desired.

Referring again to the reactor 3 used catalyst of diminished activity is continuously drawn o3 from the bottom thereof through a pipe I2 com-A municating with a branch pipev i3 leading to a cooler it from which the used catalyst is discharged into a scrubber I5. 'In the cooler I4 the temperature of the withdrawn catalystl may be reduced to a temperaturein the range about 70 to 150 F. or even to a lower temperature if desired.

Instead of withdrawing the used catalyst from the bottom of the tower it may be withdrawn from the upper portion of the tower through a pipe i8 which likewise communicates with the branch pipe I3.

The scrubber l5 may be a packed tower and is operated so that the used catalyst descends through the tower countercurrently to a rising body of wash solvent which in this case is normal butane. f

The oily material dissolved in or mixed with the normal butane is continuously withdrawn from the top of the scrubber I5 through a pipe Il which communicates with the previously mentioned pipe 'i'. Since the catalyst drawn oi from the reactor 3 will contain some hydrogen chloride, it follows that the liquid stream withdrawn from the top of the scrubber may contain substantial Therefore, it is advantageous to pass this stream directly to the previously mentioned stripper 8 wherein .the retained hydrogen chloride may be recovered for recycling to the reactor 3. The normal butane and oily material is withdrawn from the bottom of the stripper along with the isomerized hydrocarbon mixture which is passed to the fractionator Il. A

Thus. in the fractionator I I a side stream conot normal butane may be produced 'and the normal butane thus recycled throughs pipe 20 communicating with the previously mentioned scrubber lil.

The washed catalyst from which oily material has been removed is continuously drawn off from the bottom' of the scrubber I5 through a pipe 2| and may be directed through a branch pipe 22 communicating with pipe 23 by which means the washed catalyst is recycled to the reaction tower. If desired the washed complex catalyst may be subjected to a repressuring' step wherein hyi drogen chloride is injected into the complex so that the complex is saturated with hydrogen chloride under the conditions of temperature and pressure prevailing within the reactor 3 prior to introduction to the reactor. In this case the washed complex is passed through a pipev 24 to a repressuring vessel 25 to which hydrogen chloride is added from a source not shown through a pipe 26. From the vessel 25 the complex saturated with hydrogen chloride is discharged into the previously mentioned pipe 23 for return to the reactor 3. c

Since a small amount of aluminum chloride is consumed during continued operation of the process`itis contemplated adding a small amount of aluminum chloride continuously or intermittently to the reactor 3 so that the complex catalyst in catalyst may be continuously or intermittently sisl in the scrubbing operation I5 may be either lower or higher than that prevailing in the reactor 3. For example, when isomerizing higher molecular weight hydrocarbons such as pentane, hexane, etc., the pressure prevailing in the reactor 3 may be relatively low. Consequently the pressure prevailing in the scrubber l5 may be substantially higher than 'that prevailing in the reactor" 3 in order to maintain the butane in a liquefied condition. If a higher pressure prevails in the scrubber i5 it may be desirable to pass the eilluent butane mixture to a separate fractionating unit.

Whilethe scrubbing treatment as desired above is eifected without the addition of any promoter beyond that already present in the complex cata- 4 lyst as withdrawn from the reactor 3,'nevertheless it iswithin the scope of the invention to'effect the normal butane ytreatment in the presence of a small amount of added promoter if desired. Thus, the normal butane treatment may actually be carried out under conditions such that isomerformed complex, such complex may be prepared y and extracted therefrom. f The wash liquid containing dissolved impurities in a mixer 30 wherein kerosene or a kerosene, fraction is reacted in the presence of HC1 with aluminum chloride conducted from a 'storage hopper 3l. The resulting complex is passed to a vent chamber 32 and from there to the previously mentioned scrubber i5.

Fig. 2 illustrates a method ofv ow which may be useful in carrying `out either an alkylation reaction or an isomerization reaction although it will lbe described with reference to isomerization speciflcally.

The feed hydrocarbon is introduced through a pipe 50 andpassed through a heater 5I wherein it is raised to the reaction temperature. The hot Ifeed mixture is then introduced to a reactor 52 which is ofthe agitator type. As indicated it is Y provided with an interior cylindrical section Asa having a propeller 54 by whichmeans the liquid contents of the vessel 52 are forced downwardly` A portion of the reaction mixturel is continuously drawn oil' through a pipe lilll to a scrubberV 'El and may, if desired, be cooled during passage through a cooler 82 to a temperature of about 70 to'150 F.

The cooled mixture is introduced to the intermediate portion of the vessel 6I, which vessel is advantageously of substantial height to permit settling. The catalyst separates as a catalyst phase in the bottom portion of the vessel 6i while the hydrocarbons collect as a hydrocarbon phase in the upper portion.

The catalyst phase is continuously drawn off from the bottom of the vessel 6I through a pipe -83 by which means it is returned to the bottom of the reactor 52 for further use as a catalyst. `As indicated, make-up catalyst may be injected from a pipe 64 into therecycling stream of catalyst, On the other hand the make-up catalyst may be injected in the entering hydrocarbon feed stream. As indicated the body of catalyst phase accu-4 mulating in the bottom of the vessel 6i is sub- Jected to continuous scrubbing with a washllquid introduced to the bottom of the scrubber through a pipe B5 at a temperature of about 70 t0 150 F.

'I'he wash liquid may be a low Boiling parailln hydrocarbon such as normal or -iso butane or a solvent such as' methylene chloride, and is in-` troduced in substantial amount, for example, in the proportion of about 3 or 4 volumes of wash liquid per volume of catalyst phase. In this way the -tarry material and other impuritiesv associated with the complex are continuously washed -are then conducted through a pipe I0 A'to a frac-- tionator llfor separation into additional fractions.- Thus, the fraction removed from the top ofthe fractionator Il may'comprise isomerized hydrocarbons.

The hydrocarbon used as a washing liquid andY v depending upon its boiling range may be removed as an independent fraction from the proper point in the fractionation system and returned tothe scrubber through the previously mentioned pipe 65. l

When the process is used for alkylation as, for example, the alkylation of isobutane with a klotr boiling olefin, such as ethylene or p'ropylenef it will, of course, be understood that the feed mixture entering the system through the pipe 50 will contain the isoparailin and olefin constituents of the feed in the proper proportion, which means that the isoparailin is usually in substantial molecular excess oyer the olefin.4

The appropriate temperature conditions willbe v maintained in the reaction vessel which in the case of an 'alkylation reaction' is relatively lower than prevails for isomerization.

ploying aluminum halides.

- drogen chloride and hydrogen bromide.

' -Also the complex may be prepared initially by reacting the metallic halide with relatively low boiling hydrocarbons other than kerosene, al- 1 though saturated aliphatic' hydrocarbons in the boilingrange of gasoline and kerosene are prey ferred. In a continuous process, asmall amount of metallic halide is continuously yor ysubstantially this continuously added to the reaction zone, a small amount of used complex being withdrawn. The ladded metallic halide apparentlyA entersinto complex formation with a portion of the entering feed hydrocarbon or with hydrocarbon fragments thereof, so -that after atime the effective catalyst may consist entirely of complex formedin situ.

a',l normally liquid hydrocarbon boiling below about 450 to 500 F.

Obviously many modifications and-yariationsof the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and, therefore, only such limitations 'y should be imposed as are indicated in the ap-v pended claims.

Iclaim: 1. In a process for effecting conversion of hy,-

drocarbons involving reactionssuch as alkylation V and isomerization by contact with an aluminum halide hydrocarbon complex, the steps comprising-'continuously passing a stream of feed hydrocarbons to a reaction zone, subjecting said hydrocarbons therein to contact with liquid aluminum halide-hydrocarboncomplex catalyst in the presence of hydrogen halide promoter under predetermined conditions of pressure and elevated temperature such that substantial conversion is effected. continuously withdrawing reacted hydrocarbons containing some promoter from the reaction zone. .passing withdrawn reacted hydro- Mention .has been specifically made of em- However, it is con` templated that the catalyst may be a complexof other metallic halides selected from the halides of the metals. of groups 2, 3, 4, 5 and .8 of the' periodic system; Suitable promoters include hy- `withdrawn mixture of solvent,

carbons to a stripping zone, withdrawing used complex contaminated with inactive material the tower countercurrently to and in intimate contact with a rising body of wash solvent liquid introduced to the lower portion of the tower from an external source, displacing inactive ma- Y terial and promoter from said complex in the tower, withdrawing scrubbed complex from the lower portion of said tower, recycling withdrawn scrubbed complex to the reaction zone, withdrawing irom the upper portion of the tower wash solvent mixed with inactive material and promoter removed from the complex, passing inactive material and promoter to the aforesaid stripping zone, effecting removal therein of promoter from said mixture to produce a stripped mixture of hydrocarbons and solvent. recycling removed promoter to said reaction zone, removing solvent from resulting stripped mixture, and recycling removed` solvent to said scrubbing tower.

2. The method according to claim v`1 in which the wash solventis a saturated aliphatic hydrocarbon having from 3 to 5 carbon atoms per molecule.

3. The method according to claiml 1 in which the scrubbed complex is saturated with hydrogen halide promoter under said predetermined conditions of temperature and pressure prior to return to the reaction zone.

4. A lcontinuous method of isomerizing normal butane which comprises passing a stream of normal butane to areaction zone, subjecting normal butane therein while in liquid phase to contact with liquid aluminum halide-hydrocarbon complex catalyst in the presence ot hydrogen halide promoter under predetermined conditions orpi-essure and elevated temperature in the range o about 180 to 230 F, such that substantial iso-` merization of normal butane is effected. continuously withdrawing a stream of isomate hydrocarbons containing promoter from' the reaction zone, passing said stream of isomate to a stripping` zone, separately withdrawing from the ref action zone used complex contaminated with inremoving from the top of the in said stripping zone active material formed Aduring said isomerization and containing promoter,'\ passing withdrawn complex to the upper portion of a scrubbing tower, introducing to the lower portion of the scrubbing tower a stream oi normal butane in liquid phase and substantially free from promotencausing the normal butane to rise through the descending complex'in the scrubbing tower at a temperature in the range about 70 to 150 F., scrubbing tower a stream oi normal butanecontaining promoter and material removed from the complex, passing s'aid removed normal butane stream to the aforesaid stripping zone, sbjecting the removed normal butane stream and the aforesaid isomate stream to stripping in the presence of each other to remove promoter and produce a stripped hydrocarbon mixture, thereafter subjecting resulting stripped hydrocarbon mixture to fractionation inea fractionating zone, separately discharging visobutane` and normal butane from the iractionating zone, recycling dis- 1 charged normal butane in part to said scrubbing to, removing from the the scrubbed complex is saturated with hydrogen halide promoter undefsaid predetermined conditions of temperature and pressure prior to re- 40 turn to the reaction 

